EXCHANGE 


THE    PREPARATION    OF   SUBSTITUTED 

ALPHA  HALOGEN  BENZYL  BENZOATES, 

AND  A  STUDY  OF  THE   REACTIONS  OF 

THESE  COMPOUNDS 


BY 


HERBERT  EPHRAIM  FRENCH 

A.  B.  Morningside  College,  1915 
M.  A.  University  of  Illinois,  1917 


THESIS 


Submitted  in  Partial  Fulfillment  of  the  Requirements  for  the 

Degree  of 
DOCTOR  OF  PHILOSOPHY 

IN  CHEMISTRY 

IN 

THE  GRADUATE  SCHOOL 
OF  THE 

UNIVERSITY  OF  ILLINOIS 

1920 


(Reprinted  from  the  Journal  of  the  American  Chemical  Society, 
Vol.  XLIII       No.  3       March,  1921) 


THE    PREPARATION    OF   SUBSTITUTED 

ALPHA  HALOGEN  BENZYL  BENZOATES, 

AND  A  STUDY  OF  THE   REACTIONS  OF 

THESE  COMPOUNDS 


BY 


HERBERT  EPHRAIM  FRENCH 

A.  B.  Morningside  College,  1915 
M.  A.  University  of  Illinois,  1917 


THESIS 

* 
Submitted  in  Partial  Fulfillment  of  the  Requirements  for  the 

Degree  of 
DOCTOR  OF  PHILOSOPHY 

IN  CHEMISTRY 

IN 

THE  GRADUATE  SCHOOL 
OF  THE 

UNIVERSITY  OF  ILLINOIS 
1920 


(Reprinted  from  the  Journal  of  the  American  Chemical  Society, 
Vol.  XLIII       No.  3       March,  1921) 


ACKNOWLEDGMENT. 

This  investigation  was  undertaken  at  the  suggestion  and  under 
the  direction  of  Professor  Roger  Adams. 

The  writer  wishes  to  acknowledge  his  indebtedness  to  Professor 
Adams  for  the  interest  he  has  shown,  and  for  the  many  helpful 
suggestions  given  during  the  course  of  this  investigation. 


444259 


VII.     VITA 

The  writer  of  this  thesis  was  born  in  Ireton,  Iowa,  November  13, 
1889.  He  attended  the  grade  schools  at  that  place,  but  received  his 
high  school  education  in  Sioux  City,  Iowa.  In  September,  1910,  he 
entered  Mforningside  College,  from  which  he  graduated  with  the  de- 
gree of  Bachelor  of  Arts,  in  June,  1915.  During  the  summer  of 
1915,  he  attended  the  University  of  Chicago,  taking  work  in  the 
Department  of  Chemistry,  and  in  September  of  the  same  year,  he 
took  up  graduate  work  in  Chemistry  at  the  University  of  Illinois, 
He  received  the  degree  of  Master  of  Arts  from  that  Institution  in 
June,  1917.  During  the  time  from  February,  1916,  to  June,  1920, 
he  held  the  position  of  Assistant  in  Chemistry  at  the  University 
of  Illinois.  He  is  a  member  of  Sigma  Xi,  Phi  Lambda  Upsilon,  and 
Alpha  Chi  Sigma. 


l&eprinted  from  the  Journal  of  the  AmericanChemical  Society, 
Vol.  XLIII.     No.     3.       March,  1921.] 


[CONTRIBUTION  FROM  THE  CHEMICAL  LABORATORY  OF  THE  UNIVERSITY  OF  ILLINOIS.] 

THE  REACTION  BETWEEN  ACID  HALIDES  AND  ALDEHYDES.  II. 

BY  H.  K.  FRENCH  WITH  ROGER  ADAMS. l 

Received  January   10,   1921. 

In  an  earlier  paper  from  this  laboratory,2  the  fact  was  brought  out  that 
many  aromatic  aldehydes  and  aromatic  acid  halides  react  readily  to 
form  halogenated  benzyl  benzoates  and  a  study  of  a  number  of  the  re- 
actions of  these  condensation  products  was  made.  In  the  present  com- 
munication this  work  has  been  extended. 

It  has  been  shown  that  the  reaction  between  aromatic  acid  halides  and 
the  aromatic  aldehydes  is  very  general.  The  previous  work  indicated 
that  in  a  few  instances  perhaps,  certain  aromatic  aldehydes  would  not 
condense  with  certain  aromatic  acid  halides  to  give  the  expected  deriva- 
tives. This  conclusion  resulted  from  the  fact  that  solid  products  could  not 
be  isolated  although  from  the  nature  of  the  substituents  solid  products 
might  be  expected.  The  oils  which  were  produced  always  decomposed 
when  vacuum  distillation  was  attempted  so  that  it  was  impossible  to 
determine  whether  a  definite  substance  existed  or  whether  merely  a 
mechanical  mixture.  By  treating  these  oily  reaction  mixtures  with 
pyridine,  solid  addition  compounds  of  pyridine  and  the  aldehyde-acid 
halide  products  were  formed  and  easily  purified.  Thus  it  was  shown 
that  a  reaction  actually  had  taken  place  in  these  instances  and  the  re- 
sulting products  were  oils.  Moreover  the  aldehyde-acid  halide  condensa- 
tion products  which  were  solids  but  too  unstable  to  purify  and  analyze 
could  be  isolated  in  the  form  of  stable  pyridine  addition  products.  These 
same  pyridine  addition  products  could  be  made  also  by  first  treating 
pyridine  with  an  acid-halide  and  then  adding  the  aldehyde. 

1  This  communication  is  an  abstract  of  work  carried  out  by  H.  E.  French  in  partial 
fulfilment  for  the  degree  of  Doctor  of  Philosophy  at  the  University  of  Illinois. 

2  THIS  JOURNAL,  40,  1732  (1918). 


652  H.    K.    FRENCH    WITH    ROGER    ADAMfe. 


C5H6N\ 
p 

C5H5NXCOR  +  RCHO/ 
Trimethylamine  formed  addition  products  in  a  similar  manner  to  pyridine, 
and  presumably  any  other  aliphatic  tertiary  amine  would  react  similarly. 

The  large  number  of  aromatic  aldehydes  and  aromatic  acid  halide 
compounds  produced,  allowed  definite  conclusions  to  be  drawn  in  regard 
to  the  ease  of  formation.  In  general  the  acid  halides  or  aldehydes  con- 
taining a  chlorine,  bromine,  iodine  or  nitro  group  reacted  more  slowly 
to  give  addition  products  than  those  acid  halides  and  aldehydes  which 
were  unsubstituted  or  contained  methyl  or  methoxy  groups.  On  the 
other  hand  the  former  class  yielded  much  more  stable  products  than  were 
formed  in  the  latter  class.  If  a  methoxy  or  methyl  group  was  present  the 
resulting  halogenated  esters,  even  though  the  phenyl  groups  contained  a 
halogen  or  nitro  group  in  addition,  were  quite  unstable  substances. 
Aromatic  aldehydes  did  not  react  as  rapidly  with  aromatic  acid  chlorides 
as  with  the  corresponding  acid  bromides.  It  appeared,  moreover,  that 
with  the  acid  chlorides  the  addition  reactions  did  not  run  so  nearly  to 
completion  as  with  the  acid  bromides;  in  many  cases,  the  acid  chlorides 
and  aldehydes  gave  only  semi-solid  reaction  masses  even  after  several 
days'  standing. 

It  seems  apparent  that  the  reaction  between  the  acid  halides  and 
aldehydes  to  form  the  halogenated  esters  is  an  equilibrium  reaction,  the 
equilibrium  point  depending  on  the  nature  of  the  initial  substances  and 
of  the  product.  Sometimes  the  reactions  ran  almost  to  completion,  in 
other  cases  only  part  way.  The  latter  type  was  particularly  noticeable 
with  the  acid  chlorides.  Many  of  the  pure  halogenated  esters,  although 
kept  in  a  dry  place  changed  within  a  few  days  to  a  semi-solid  mass  which 
appeared  similar  to  that  formed  by  the  addition  of  the  acid  halide  to  the 
aldehyde.  A  trace  of  zinc  chloride  greatly  speeded  up  the  reactions  and 
caused  the  equilibrium  point  to  be  reached  in  a  comparatively  short  time. 
The  tendency  of  these  halogenated  esters  to  dissociate  accounts  for  a 
number  of  their  reactions,  especially  those  which  might  be  expected  pro- 
viding these  compounds  were  merely  mixtures  of  acid  halide  and  aldehyde. 

A  preliminary  study  of  the  reactions  of  these  addition  compounds  was 
made  by  Adams  and  Vollweiler.1  It  was  found  that  with  water,  the 
addition  compounds  behaved  as  a  simple  mixture  of  acid  halide  and  alde- 
hyde producing  hydrobromic  acid,  organic  acid  and  aldehyde;  with 
alcohol,  a  similar  reaction  took  place,  with  the  formation  of  an  ester, 
aldehyde  and  hydrobromic  acid;  with  ammonia  in  dry  ether  solution 
there  resulted  an  acid  amide,  aldehyde  and  ammonium  bromide;  with 
1  Adams  and  Vollweiler,  THIS  JOURNAL,  40,  1732  (1918). 


REACTION   BETWEEN   ACID   HAUDES   AND   ALDEHYDES.      II.  653 

aniline,  the  organic  acid  and  phenyl-bromomethyl  aniline  in  practically 
quantitative  yields  formed  according  to  the  following  equation: 
CeHsCHBrOCOCeHs  -f  C6H5NH2  — >  CeHsCHBrNHCeHg  +  C6H5COOH 

|    NaOH 

C6H5CH  :  NC6H5  +  NaBr  +  H2O 

In  the  present  research,  the  action  of  different  amines  has  been  investi- 
gated; o-  and  ^-chloro-anilines,  o-  and  ^-toluidines  all  give  analogous  re- 
sults to  aniline  itself.  As  a  type  of  primary  aliphatic  amine,  methyl 
arnine  was  chosen.  In  dry  ether  solution,  bromomethyl  benzoate  with 
this  amine  yields  methyl  benzamide,  methyl  amine  hydrobromide  and 
benzylidene  methyl  amine. 
C6H6CHBrOCOC6H5  +  3CH3NH2  — > 

C6H5CONHCH3  +  CH3NH2  •  HBr  -f  C6H5CH  =  NCH3  +  H2O. 
Secondary  aliphatic  amines,  such  as  diethyl  amine,  give  a  mixture  of 
disubstituted  acid  amide,  aldehyde  and  salt  of  the  amine. 
CeHsCHBrOCOCeHs  +  2(C2H5)2NH  — > 

C6H5CON(C2H5)2  +  C6H5CHO  +  (C2H5)2NH.HBr. 

Tertiary  aliphatic  amines,  such  as  trimethyl  amine,  give  addition  com- 
pounds; pyridine  acts  in  a  similar  manner  as  has  already  been  mentioned. 
With  secondary  and  tertiary  aromatic  amines,  complex  substances  be- 
longing to  the  triphenyl  methane  series  are  produced. 

These  halogenated  esters  in  dry  ether  react  with  zinc  or  copper  powder 
to  give  condensation  products  which  are  derivatives  of  the  dibenzoate  of 
hydrobenzoin.1 

2C6H6CHBrOCOC6H5  +  Zn  —^  (CelfcCHOCOCeHs)*  -f  ZnBr2. 
Many  side  reactions,  however,  take  place,  so  that  the  yields  seldom  are 
greater  than  20%. 

The  addition  compounds  react  with  potassium  cyanide,  alkali  salts  of 
organic  acids  or  potassium  hydroxide  to  give  more  or  less  complete  hy- 
drolysis. Definite  compounds  from  these  reactions  have  not  been  isolated. 

Experimental. 

To  prepare  the  addition  compounds,  equimolecular  amounts  of  the  acid  halide 
and  aldehyde  were  mixed  and  allowed  to  stand  at  room  temperature  in  a  tightly  stop- 
pered flask.  More  or  less  heat  was  invariably  evolved  and  in  the  course  of  from  a  few 
minutes  up  to  several  days,  the  mixtures  became  solid  or  semi-solid  and  did  not  change 
on  further  standing.  The  products  were  washed  with  a  little  dry  ether  or  petroleum 
ether,  powdered  and  then  recrystallized.  It  was  noticeable  that  the  acid  bromides 
in  most  cases  formed  solids  with  the  aldehydes  while  in  general,  the  acid  chlorides  formed 
semi-solids  with  the  aldehydes.  The  times  for  the  reactions  given  in  the  following 
tables  represent  the  maximum  time  necessary  after  which  no  further  change  in  the  mix- 
ture was  noticed.  When  a  small  amount  of  anhydrous  zinc  chloride  was  added,  the 
time  required  for  reaching  the  end  of  the  reaction  was  greatly  diminished. 

The  compounds  and  their  constants  and  analyses  are  given  in  the  following  table. 

1  -Ber.,  15,  1818  (1882);  17,  911  (1884). 


654 


H.    E.    FRENCH   WITH   ROGER   ADAMS. 


So     8 


00          »-i 
CO  O3 


3     cS     2     8 

S        S        ° 


o 


g 


o 

S     $     S3 


<N  (N  CO  T-I 

4     d     d     i 


S 
35 

9  S 

^}^  CO 

t^*  CD 

0^  "5 

^H  CM 


1  I 


REACTION   BETWEEN   ACID   HALIDES   AND   ALDEHYDES.      II. 


655 


.9 


8     S 


CO 


656  H.  E.  FRENCH  WITH  ROGER  ADAMS. 


Phenyl  Chloromethyl  Benzoate, 

Upon  mixing  benzoyl  chloride  and  benzaldehyde  together  with  a  small  piece  of 
fused  zinc  chloride,  a  reaction  took  place  at  once  and  heat  was  developed.  No  solid 
formed,  however,  even  after  long  standing  and  thorough  chilling.  The  resulting  oil 
was  fractionated  as  follows: 

1st  fraction,  boiling  77-81°  at  15  mm. 

2nd  fraction,  boiling  84-86°  at  15  mm. 

3rd  fraction,  boiling  205-208°  at  15  mtn. 

The  first  and  second  fractions  proved  to  be  benzaldehyde  and  benzoyl  chloride,  respiv 
tively.     The  third  fraction  which  solidified  proved  to  be  benzoic  anhydride. 

In  addition  to  the  above  chlorinated  esters,   (Nos.  22-28  in  the  table) 
those  produced  from  cinnamyl  chloride  and  anisaldehyde  as  well  as  from 
cinnamyl  chloride  and  piperonal  and  methyl   vanillin  were-  made.     Both 
were  solids  but  unstable  so  that  they  were  not  purified  for  "analysis. 
Compounds   Formed   from   Pyridine   and   the   Acid   Halide-Aldehyde 

Condensation  Products. 

Phenyl-bromomethyl  Benzoate  and  Pyridine,  C6H5XBrCH(C«H6)OCOC«H6.- 
phenyl-bromomethyl  benzoate  was  treated  with  excess  of  pyridine.  It  went  into  solution 
slowly,  but  there  was  no  evidence  of  a  reaction.  On  standing,  however,  crystals  began 
to  deposit  and  soon  a  heavy  precipitate  had  formed.  The  solid  material  was  tilUrrd 
off  and  purified  by  dissolving  in  absolute  alcohol  and  precipitating  with  dry  ether.  It 
melted  at  180°  with  decomposition,  was  very  soluble  in  water  and  gave  a  neutral  solu- 
tion. This  solution  gave  an  immediate  precipitate  of  silver  bromide  on  the  addition 
of  silver  nitrate. 

Analyses.  Subs.,  0.5954,  0.5934:  17.14,  17.14  cc.  0.0934  A'  igNQ  Calo.  for 
C19H1002NBr:  Br,  21.62.  Found:  21.50,  21.58. 

The  same  compound  was  also  made  by  adding  1  mol  of  beuzoyl  bromide  to  J  .5  nu-U  •<- 
of  pyridine.  The  resulting  solid  addition  compound  was  pulverized  and  to  it  1  mol  of 
benzaldehyde  was  added.  An  immediate  reaction  took  place  and  the  solid  suhstamv 
just  described  above  was  produced. 

Phenyl-chloromethyl  Benzoate  and  Pyridine,  CfiHoNClCHtCtHOOCOQH*.  -On 
mixing  equimolecular  amounts  of  benzoyl  chloride  and  benzaldehyde,  an  immediate 
reaction  took  place.  When  cold,  the  resulting  oil  was  poured  into  one  mol  of  pyridine 
In  about  half  an  hour,  the  mixture  had  become  a  pasty  solid.  The  solid  material  was 
filtered  off  and  purified  by  dissolving  in  absolute  alcohol  and  precipitating  with  dry 
ether.  It  then  melted  at  192°  with  decomposition. 

Analyses.  Subs.,  0.6210,  0.5910:  LS.67,  17.81  cc.  of  0.1022  N  AgNOs.  Calc.  for 
C19H16O2NC1:  Cl,  10.90.  Found:  10.90,  10.93. 

A  mixture  of  10  g.  (one  mol)  of  benzoyl  chloride  and  5.6  g.  (one  raol)  of  pyridine 
was  allowed  to  stand  overnight.  Only  a  few  crystals  had  separated  by  that  time. 
When  7.5  g.  (one  mol)  of  benzaldehyde  was  added,  a  reaction  took  place  at  once  with 
the  liberation  of  considerable  heat.  The  solid  product  was  purified  as  already  men- 
tioned by  dissolving  in  absolute  alcohol  and  precipitating  with  dry  ether,  and  had  the 
same  m.  p.,  192°. 

p  -  Methoxyphenyl-bromomethyl  -  p  -  Nitrobenzoate  and  Pyridine,  CiH5NBrCH- 
(CeH4OCH3)(£)OCOC6H4NO2(£).-—  />-Nitrobenzoyl  bromide  reacted  with  anisaldehyde  to 
give  a  solid  product  in  about  2  minutes.  This  material  was  pulverized  and'added  in 
small  amounts  to  an  excess  of  pyridine.  Complete  solution  took  place,  followed  in  a 

1  Compt.  rend.,  31,   113  (1850);  Ann..  154,  347  (1870). 


REACTION   BETWEEN   ACID   HALIDES   AND   ALDEHYDES.      II.  657 

few  minutes  by  the  separation  of  a  solid  product.  This  was  purified  by  dissolving  in 
absolute  alcohol  and  precipitating  with  dry  ether.  After  drying  in  vacuo  over  sulf uric 
acid,  the  product  melted  at  126-128°. 

Analyses.  Subs.,  0.6097:  13.65  cc.  of  0.1022  N  AgNO,.  Calc.  for  Q»HnO5N2Br: 
Br,  17.97.  Found:  18.17. 

A  semisolid  product  was  obtained  when  the  o-methylbenzoyl  bromide  and  benzal- 
dehyde  were  mixed  and  allowed  to  stand  overnight.  This  was  added  to  one  mol  of 
pyridine,  and  the  solid  product  thus  obtained,  after  being  purified  by  dissolving  in 
absolute  alcohol  and  precipitating  with  dry  ether,  melted  at  206°  with  decomposition. 

Analyses.  Subs.,  0.6630,  0.7751:  17.08,  19.91  cc.  0.1022  N  AgNO3.  Calc.  for 
CwHigOaNBr:  Br,  20.83.  Found:  21.06,  21.00. 

Reactions  of  Phenyl  Bromomethyl  Benzoate  with  Amines. 

Phenyl  Bromomethyl  Benzoate  and  Methyl  Amine. — A  heavy  white  precipitate 
of  methylamine  hydrobromide  began  to  form  almost  at  once,  when  dry  methylamiuc 
was  passed  into  a  solution  of  the  phenyl-bromo-methyl  benzoate  in  dry  ether.  About 
3  moles  of  the  amine  was  added  and  the  mixture  then  allowed  to  stand  overnight. 
After  filtering  off  the  precipitate,  the  ether  was  evaporated  and  the  oil  obtained  was 
separated  into  2  fractions  by  distillation  in  vacuo.  The  lower  boiling  fraction  was  re- 
distilled under  ordinary  pressures,  and  proved  to  be  benzylidene  methylamine,  b.  p. 
180-181°.  The  higher  boiling  fraction  solidified  and  was  methyl  benzamide,  C«H6- 
CONHCH8,  m.  p.  78-79°. 

Phenyl-bromomethyl  Benzoate  and  Diethylamine. — Phenyl-bromomethyl  ben- 
zqate  when  treated  with  diethylamine  in  the  manner  just  described  under  methyl- 
amine gave  an  oil,  which,  fractionated  in  vacuo,  gave  (1)  boiling  at  88°  at  35  mm.;  (II) 
boiling  at  160-175°  at  35  mm.  On  redistillation  under  ordinary  pressures,  the  2  frac- 
tions were  found  to  be  benzaldehyde,  boiling  at  179-182°,  and  diethyl  benzamide,  boil- 
ing at  278-282°. 

Phenyl-bromomethyl  Benzoate  and  Trimethyl-amine,  (CH3)8NBrCH(C«Ho)- 
OCOC«Hf. — When  dry  trimethyl-amine  was  passed  into  an  absolute  ether  solution  of 
phenyl-bromomethyl  benzoate,  a  heavy  white  precipitate  began  to  form  at  once.  When 
3  moles  of  the  amine  had  been  added,  the  thick  mass  resulting  was  filtered  and  the  solid 
recrystallized  from  alcohol.  It  melted  at  136-137°. 

The  white  solid  was  completely  soluble  in  water,  and  this  solution  when  treated 
with  sodium  hydroxide  gave  off  trimethyl-amine.  The  odor  of  benzaldehyde  could 
also  be  detected.  Acidification  of  the  alkaline  solution  precipitated  benzoic  acid. 

Analyses.  Subs.,  0.2632,  0.2042:  AgBr,  0.1400,  0.1080.  Calc.  for  CwHwOsNBr: 
Br,  22.85.  Found:  22.63,  22.50. 

Phenyl-bromomethyl  Benzoate  and  o-Chloro-aniline,  CeHsCHBrNHCeH^Cl (<?).— 
Phenyl-bromomethyl  benzoate  and  o-chloro-aniline  reacted  immediately  and  produced 
a  yellow  solid.  By  treatment  with  several  portions  of  dry  ether,  the  benzoic  acid  pro- 
duced as  a  by-product  was  extracted.  The  yellow  solid  remaining  was  analyzed. 

Analyses.  Subs.,  0.5429:  17.84  cc.  0.1022  N  AgNO3.  Calc.  for  CuHuNBrCl: 
Br,  26.98.  Found:  26.86. 

Some  of  this  substance  was  treated  with  20%  sodium  hydroxide  solution,  extracted 
with  ether,  and  the  ether  extract  dried  over  calcium  chloride  and  evaporated.  The 
solid  remaining  was  found  to  melt  at  54°.  A  mixed  melting  point  with  some  benzyl- 
idene-0-chloroaniline  (prepared  from  benzaldehyde  and  0-chloro-aniline)  was  taken 
and  found  to  be  54°. 

It  was  found  that  the  yellow  solid  was  completely  hydrolyzed  by  water,  so  that 
if  it  were  first  dissolved  in  water  and  then  sodium  hydroxide  solution  added,  o-chloro- 
aniline  was  precipitated  instead  of  benzylidene-o-chloro-amline. 


658  H.    E.   FRENCH   WITH   ROGER  ADAMS. 


Phenyl-bromomethyl  Benzoate  and  />-Chloro-aniline, 
Phenyl-bromomethyl  benzoate  and  />-chloro-aniline  were  allowed  to  react,  then  treated 
as  described  under  the  o-chloro-aniline.  Phenyl-bromomethyl-p-chloro-aniline  was 
produced  and  yielded  by  treatment  with  20%  sodium  hydroxide,  benzylidene-p-chloro- 
aniline,1  m.  p.  62°. 

Phenyl-bromomethyl  Benzoate  and  £-Toluidine,  CeHsCHBrNHC^CH,  (£).— 
Phenyl-bromomethyl  benzoate  and  />-toluidine  reacted  vigorously.  After  extraction 
of  the  benzoic  acid  with  dry  ether,  the  solid  proved  to  be  phenyl-bromomethyl-/>-tolu- 
idine. 

Analyses.  Subs.,  0.5949:  21.26  cc.  0.1022  N  AgNO,.  Calc.  for  CuH14NBr:  Br, 
28.98.  Found:  29.21. 

Phenyl-bromomethyl  Benzoate  and  Mono-ethylaniline.  —  A  dry  ether  solution  of 
phenyl-bromomethyl  benzoate  (one  mol)  was  added  to  a  dry  ether  solution  of  mono- 
ethyl  aniline  (two  mol)  and  enough  heat  was  generated  to  cause  the  ether  to  boii. 
After  refluxing  for  8  hours,  the  ether  was  decanted  from  the  dark  red  viscous  mass  in 
the  flask.  The  ether  was  extracted  successively  with  sodium  carbonate  and  dilute 
hydrochloric  acid,  which  yielded  benzoic  acid  and  mono-ethylaniline  respectively. 
Evaporation  of  the  ether  furnished  a  small  amount  of  benzaldehyde. 

Oxidation  of  the  red  viscous  material  with  lead  dioxide  and  hydrochloric  acid 
yielded  a  green  solution.  An  alcohol  solution  of  the  gummy  material  was  red  in  direct 
light  and  green  in  reflected  light  With  mercuric  chloride  this  solution  produced  a  white 
precipitate  which  turned  blue  on  drying.  These  properties  correspond  to  those  expected 
of  the  dye  from  diethyl-diamino-triphenyl  carbinol.* 

Phenyl-bromomethyl  Benzoate  and  Diphenylamine.—  When  a  dry  ether  solution 
of  one  mol  of  phenyl-bromo-methyl  benzoate  and  a  dry  ether  solution  of  two  mols  of 
diphenylamine  were  mixed,  a  colorless  precipitate  began  to  form  almost  at  once.  After 
standing  for  1.5  hours  a  green  gummy  deposit  formed.  The  solution  was  filtered,  and 
the  residue  washed  with  ether.  By  using  the  method  of  Meldola,1  crystals  of  the  dye 
from  diphenyl-diamino-triphenyl  carbinol  were  obtained. 

Phenyl-bromomethyl  Benzoate  and  Dimethylaniline.  —  A  dry  ether  solution  of 
one  mol  of  phenyl-bromomethyl  benzoate  and  a  dry  ether  solution  of  two  mols  of  di- 
methylaniline  were  mixed  and  refluxed  for  9  hours.  A  considerable  amount  of  a  green 
viscous  mass  separated.  After  evaporating  the  ether,  the  material  was  steam  distilled. 
As  much  water  as  possible  was  then  distilled  off  from  the  residue  and  an  attempt  was 
made  to  recrystallize  the  green  mass  remaining,  but  without  success.  The  material 
was  then  reduced  with  zinc  and  hydrochloric  acid  and  the  leuco  base  of  malachite  green 
was  obtained.  On  recrystallization  from  alcohol,  this  material  melted  at  92-93°. 

Reactions  of  Phenyl-Bromomethyl  Benzoate  and  Substituted  Benzoates 

with  Metals. 

Phenyl-bromomethyl  Benzoate  and  Zinc;  Formation  of  Dibenzoyl-hydrobenzoin, 
(CaHsCHOCOCeHeV  —  To  an  absolute  ether  solution  of  phenyl-bromomethyl  benzoate 
(one  mol)  zinc  dust  (12  mol)  was  added  in  small  portions.  The  flask  was  well  shaken 
during  the  addition.  The  solution  was  then  filtered  and  the  zinc  extracted  twice  with 
ether,  then  twice  with  hot  benzene.  Upon  evaporation  of  the  extraction  liquors,  the 
product,  dibenzoyl-hydrobenzoin  in  20%  yields  was  obtained.  It  melted  at  246-247*, 
after  one  crystallization  from  benzene. 

On  evaporation  of  the  original  ether  solution,  a  tar  was  obtained  which  yielded 

1  Ber.,  34,  829  (1901). 

8  Ann.  Spl,  3,  363  (1865). 

«  J.  Chem.  Soc.,  41,  192  (1882). 


REACTION   BETWEEN  ACID   HAUDES  AND  ALDEHYDES.      II.  659 

benzole  acid  when  extracted  with  50%  alcohol.  Attempts  to  recrystallize  the  resin 
remaining  were  unsuccessful. 

^-Bromophenyl-bromomethyl  Benzoate  and  Zinc;  Formation  of  Dibenzoyl-/>,/?-di- 
bromo-hydrobenzoin,  ((/O-BrC^CHOCOCeHe^. — An  absolute  ether  solution  of 
£-bromophenyl-bromomethyl  benzoate  was  treated  with  a  large  excess  of  zinc  dust  in 
the  same  way  as  the  phenyl-bromomethyl  benzoate.  A  16.8%  yield  of  the  dibenzoate, 
was  obtained.  After  crystallization  from  benzene,  the  product  melted  at  225°. 

A  nalyses.  Subs.,  0.0572 :  AgBr,  0.0368.  Calc.  for  C28H2oO4Br2 :  Br,  27.58.  Found : 
27.37. 

Phenyl-bromomethyl  Benzoate  and  Copper  Powder. — The  copper  powder  was 
prepared  by  adding  zinc  dust  to  a  solution  of  copper  sulfate.  It  was  filtered  off  and 
digested  with  cone,  hydrochloric  acid,  washed  with  water  and  dried  in  vacua  over  sul- 
furic  acid. 

This  reacted  with  the  phenyl-bromomethyl  benzoate  in  the  same  way  as  did  the 
zinc  dust,  producing  a  20%  yield  of  the  dibenzoate  of  hydrobenzoin. 

With  sodium,  magnesium  or  aluminum  powders,  only  negative  results  were  ob- 
tained. 

Phenyl-bromomethyl  Benzoate  and  Alkalies  or  Alkali  Cyanide. — The  reaction 
between  phenyl-bromomethyl  benzoate  and  potassium  hydroxide  or  potassium  cyanide, 
although  carried  out  under  widely  varying  conditions,  always  produced  complete  hy- 
drolysis. 

Summary. 

1.  The  reaction  between  aromatic  acid  halides  and  aromatic  aldehydes 
is  a  general  one.     Benzoyl  bromide,  benzoyl  chloride,  and  a  number  of 
their  substitution  products  have  been  condensed  with  various  aromatic 
aldehydes. 

2.  Halogen  and  nitro  groups  in  either  aromatic  nucleus  tend  to  retard 
the  speed  of  reaction,  and  usually  produce  more  stable  substances.     Methyl 
and  methoxy  groups  tend  to  hasten  the  speed  of  the  reaction,  with  the 
formation  of  less  stable  products. 

3.  The  acid  halide-aldehyde  compounds  react  with  pyridine  or  tertiary 
aliphatic  amines  to  give  stable  addition  products.     These  same  products 
are  produced  by  allowing  the  acid  halide  to  react  with  pyridine  and  then 
adding  the  aldehyde. 

4.  The  acid  halide-aldehyde  compounds  react  with  primary  and  sec- 
ondary aliphatic  amines  to  give  substituted  benzamides,  benzaldehyde, 
and  the  amine  hydrobromides.     With  primary  aromatic  amines,  the  hydro- 
bromides  of  benzylidene  or  substituted  benzylidene  anilines  together  with 
the  aromatic  acid  are  produced.     Secondary  and  tertiary  aromatic  amines 
produce  complex  compounds  in  the  triphenyl  methane  series. 

5.  The  acid  halide-aldehyde  compounds  react  with  zinc  or  copper  to 
give  esters  of  hydrobenzoin  or  substituted  hydrobenzoin. 

URBANA,  lu,. 


14  DAY  USE 

RETURN  TO  DESK  FROM  WHICH  BORROWED 

LOAN  DEPT. 

This  book  is  due  on  the  last  date  stamped  below,  or 

on  the  date  to  which  renewed. 
Renewed  books  are  subject  to  immediate  recall. 


REC'D  UD 


OCT291957 


LD  21-100m-6,'56 
(B9311slO)476 


General  Library 

University  of  California 

Berkeley 


UNIVERSITY  OF  CALIFORNIA  LIBRARY 


